Resin composition

ABSTRACT

An object of the invention is to provide a resin composition with which color tone, moldability, heat resistance, flame retardancy and mechanical properties are simultaneously attained each in a sufficient level and which is particularly excellent in color tone and less generation of foreign matter.  
     Specifically, the present invention provides a resin composition obtained by melt-kneading: (A) 99 to 1 wt. % of a functionalized polyphenylene ether resin obtained by reacting a mixture of: (a) 100 parts by weight of a polyphenylene ether, and (b) 0.01 to 10.0 parts by weight of a modifier selected from non-aromatic conjugated diene compounds, dienophile compounds having one dienophile group and precursors for these diene or dienophile compounds at a reaction temperature of from room temperature to the melting point of (a); and (B) 1 to 99 wt. % of a liquid-crystal polyester.

TECHNICAL FIELD

[0001] The present invention relates to novel resin compositions whichcan be utilized for molded products obtained by injection molding orextrusion molding, that are excellent in the balance among heatresistance, flame retardancy, moldability and mechanical properties, andparticularly, are excellent in color tone and less generation of foreignmatter.

BACKGROUND ART

[0002] In general, polyphenylene ethers are resins having excellentproperties, for example, in heat resistance, hot water resistance, sizestability and mechanical and electrical properties, but are accompaniedwith drawbacks such as poor moldability owing to their high meltviscosity, bad chemical resistance and low impact resistance. With aview to improving such defects of polyphenylene ethers, alloying themwith another resin or modification of them have conventionally beenconducted.

[0003] For example, JP-B-52-19864 (The term “JP-B” as used herein meansan “examined Japanese patent publication”) and JP-B-52-30991 propose, asa technique related to modification of polyphenylene ethers, processesfor obtaining a functionalized polyphenylene ether by, in the presenceof a radical generator, mixing a polyphenylene ether in the solutionform with styrene and maleic anhydride or another copolymerizablecompound for modification and effecting polymerization for long hours.These processes require a dissolving step, polymerizing step andmoreover, solvent removal step, leading to an increase in the cost ofequipment and energy.

[0004] JP-B-3-52486, U.S. Pat. No. 4,654,405, JP-A-62-132924 (The term“JP-A” as used herein means an “unexamined published Japanese patentapplication”), U.S. Pat. No. 4,888,397, JP-W-63-500803 (The term “JP-W”as used herein means a “published Japanese national stage ofinternational application”) and JP-A-63-54425 propose processes forobtaining a functionalized polyphenylene ether by mixing, in thepresence or absence of a radical generator, a polyphenylene ether withmaleic anhydride or another reactive compound for modification andmodifying it in a molten state by melt-kneading, etc. In theseprocesses, however, the temperature at which a polyphenylene ether canbe melt-kneaded is remarkably high and the melt viscosity of thepolyphenylene ether is considerably high. The necessity of a markedlyhigh temperature for reaction causes various problems.

[0005] A functionalized polyphenylene ether obtained by the conventionalmelt-kneading method inevitably goes through processing at a hightemperature close to its decomposition temperature so that a colorchange due to thermal deterioration occurs and this functionalizedpolyphenylene ether resin involves a problem in color tone. In addition,black foreign matter remains in the molded product as a carbide derivedfrom the polyphenylene ether, causing a lowering in insulationproperties or appearance. Accordingly, the functionalized polyphenyleneethers obtained by conventional techniques cannot meet the request ofthe industrial world sufficiently because of problems in equipment orenergy, or insufficient balance among color tone, appearance, heatresistance and mechanical properties.

[0006] As a technique related to alloying of a polyphenylene ether withanother resin, for example, U.S. Pat. No. 4,386,174 and JP-A-56-115357propose a process of mixing polymers, for example, a polyphenylene etherand a liquid-crystal polyester, thereby improving melt processability ofthe polyphenylene ether. The improvement is however not insufficient.JP-A-2-97555 proposes a process of mixing a polyarylene oxide to aliquid-crystal polyester in order to improve solder heat resistance,while U.S. Pat. No. 5,498,689 and JP-A-6-122762 propose a process ofmixing an amine-modified polyphenylene ether with a liquid-crystalpolyester. Neither process is sufficient for reconciling color tone,less generation of foreign matter, heat resistance and moldability.

[0007] An object of the invention is therefore to provide a resincomposition which can simultaneously attain color tone, moldability,heat resistance, flame retardancy and mechanical properties at asufficient level and particularly, is excellent in color tone and lessgeneration of foreign matter.

DISCLOSURE OF THE INVENTION

[0008] To achieve the above-described object, the present inventorscarried out an extensive investigation. As a result, it was found that aresin composition capable of simultaneously attaining color tone, lessgeneration of foreign matter, moldability, heat resistance and flameretardancy at a sufficient level, particularly being excellent in colortone and less generation of foreign matter can be obtained by mixing afunctionalized polypheylene ether resin obtained by a specific modifyingmethod and a liquid-crystal polyester, leading to the completion of theinvention.

[0009] The present invention therefore provides:

[0010] 1. A resin composition obtained by melt-kneading:

[0011] (A) 99 to 1 wt. % of a functionalized polyphenylene ether resinobtained by reacting a mixture of:

[0012] (a) 100 parts by weight of a polyphenylene ether, and

[0013] (b) 0.01 to 10.0 parts by weight of a modifier selected fromnon-aromatic conjugated diene compounds, dienophile compounds having onedienophile group and precursors for these diene or dienophile compoundsat a reaction temperature of from room temperature to the melting pointof (a); and

[0014] (B) 1 to 99 wt. % of a liquid-crystal polyester.

[0015] 2. The resin composition according to item 1 above, wherein thefunctionalized polyphenylene ether resin (A) has an average particlesize of 10 to 500 μm.

[0016] 3. The resin composition according to item 1 above, wherein thereaction temperature for obtaining the functionalized polyphenyleneether resin (A) is within a range of from room temperature to the glasstransition point of (a).

[0017] 4. The resin composition according to item 1 above, wherein thereaction temperature for obtaining the functionalized polyphenyleneether resin (A) is within a range of from 120° C. to 220° C.

[0018] 5. The resin composition according to item 1 above, wherein themodifier (b) is a compound having, in its molecular structure, at leastone of (i) a carbon-carbon double bond and (ii) at least one of carboxylgroup, oxidized acyl group, imino group, imide group, hydroxyl group andepoxy group.

[0019] 6. The resin composition according to item 1 above, wherein themodifier (b) is any one of maleic anhydride, maleic acid, fumaric acid,phenyl maleimide, itaconic acid and glycidyl methacrylate.

[0020] 7. The resin composition according to item 1 above, wherein themodifier (b) is maleic anhydride.

[0021] 8. The resin composition according to item 1 above, which furthercomprises (C) 0.001 to 5 parts by weight of a compound containing apolyvalent metal element based on 100 parts by weight, in total, of (A)and (B).

[0022] 9. The resin composition according to item 8 above, wherein thecompound (C) containing a polyvalent metal element is at least onecompound selected from ZnO, ZnS, SnO, SnS, zinc stearate, zinc acetateand MgO.

[0023] 10. The resin composition according to item 1 above, whichfurther comprises (D) 0.1 to 200 parts by weight of an inorganic fillerbased on 100 parts by weight, in total, of (A) and (B).

[0024] 11. The resin composition according to item 8 above, whichfurther comprises (D) 0.1 to 200 parts by weight of an inorganic fillerbased on 100 parts by weight, in total, of (A) and (B).

[0025] 12. A heat resistant part obtained by molding a resin compositionaccording to any one of items 1 to 11 above.

[0026] 13. A heat resistant part according to item 12 above, wherein theheat resistant part is for automobiles or office machines.

BEST MODE FOR CARRYING OUT THE INVENTION

[0027] The present invention is described more specifically below.

[0028] The functionalized polyphenylene ether resin (A) to be used inthe invention is obtained by reacting a mixture of (a) 100 parts byweight of a polyphenylene ether and (b) 0.01 to 10.0 parts by weight ofa modifier selected from non-aromatic conjugated diene compounds,dienophile compounds having one dienophile group and precursors forthese diene or dienophile compounds at a reaction temperature of fromroom temperature to the melting point of (a).

[0029] The polyphenylene ether (a) is a homopolymer and/or copolymercomprising a recurring unit represented by the following formula (1):

[0030] (wherein R₁ and R₄ each independently represents a hydrogen atom,a halogen atom, a primary or secondary lower alkyl group, a phenylgroup, an aminoalkyl group or a hydrocarbon oxy group; and R₂ and R₃each independently represents a hydrogen atom, a primary or secondarylower alkyl group or a phenyl group) and having a reduced viscosity (asmeasured under the conditions: 0.5 g/dl, chloroform solution, and 30°C.) of 0.15 to 1.0 dl/g. The reduced viscosity preferably is within arange of 0.20 to 0.70 dl/g, with a range of 0.40 to 0.60 being mostpreferred.

[0031] Specific examples of the polyphenylene ether includepoly(2,6-dimethyl-1,4-phenylene ether),poly(2-methyl-6-ethyl-1,4-phenylene ether),poly(2-methyl-6-phenyl-1,4-phenylene ether) andpoly(2,6-dichloro-1,4-phenylene ether). Polyphenylene ether copolymerssuch as copolymers of 2,6-dimethylphenol and another phenol (such as2,3,6-trimethylphenyl or 2-methyl-6-butylphenol) are also usable. Amongthem, poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, of which thepoly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

[0032] Examples of a manufacturing process of the polyphenylene ether(a) to be used in the invention include the process described in U.S.Pat. No. 3,306,874 wherein 2,6-xylenol is subjected to oxidationpolymerization in the presence of a complex of a cuprous salt and amineas a catalyst. The processes described in U.S. Pat. Nos. 3,306,875,3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628are also preferred as a manufacturing process of the polyphenylene ether(a).

[0033] The polyphenylene ether (a) of the invention preferably has anend structure of the following formula (2):

[0034] (wherein, R₁, R₂, R₃ and R₄ have the same meanings as R¹, R₂, R₃and R₄ in the above-described formula (1), respectively).

[0035] More preferably, the polyphenylene ether (a) of the invention hasan end structure of the following formula (2′):

[0036] (wherein, R₅ and R₅′ each represents a hydrogen atom or an alkylgroup).

[0037] In the invention, a crystalline polyphenylene ether having amelting point is used as a raw material polyphenylene ether.

[0038] Examples of literatures indicating the relation between acrystalline polyphenylene ether and its melting point include “Journalof Polymer Science, Part A-2(6), 1141-1148(1968)”, “European PolymerJournal, (9), 293-300(1973)” and “Polymer, (19), 81-84(1978)”.

[0039] In the invention, the melting point of polyphenylene ether (a) isdefined as a peak top temperature of the peak observed on atemperature-heat flow graph obtained by measurement by differentialthermal scanning calorimeter (DSC) at a heating rate of 20° C./min. Ifthere exist plural peak top temperatures, the melting point is definedas the maximum one.

[0040] Preferably, the polyphenylene ether (a) of the invention is inthe powdery form obtained by precipitation of its solution and has amelting point of 240° C. to 260° C. This powder preferably has a fusedheat (AH), determined from a peak in DSC measurement, of 2 J/g orgreater.

[0041] The modifier (b) to be used in the invention is selected fromnon-aromatic conjugated diene compounds, dienophile compounds having onedienophile group or precursors of these diene or dienophile compounds.Among them, the modifier (b) is preferably a compound having, in itsmolecular structure, at least one of (i) a carbon-carbon double bond and(ii) at least one of carboxyl group, oxidized acyl group, imino group,imide group, hydroxyl group and epoxy group. Preferred examples of themodifier include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, glycidyl methacrylate, styrene, acrylic acid,methyl acrylate, methyl methacrylate, stearyl acrylate, allyl alcoholand acrylamide. Among them, the modifier is preferably any one of maleicanhydride, maleic acid, fumaric acid, phenyl maleimide, itaconic acidand glycidyl methacrylate, with maleic anhydride being most preferred.

[0042] In the invention, the modifier (b) is added in an amount of 0.01to 10.0 parts by weight, preferably 0.1 to 5.0 parts by weight, morepreferably 0.5 to 3.0 parts by weight based on 100 parts by weight ofthe polyphenylene ether (a). When the amount of the modifier (b) is lessthan 0.01 part by weight, an amount of a functional group isinsufficient. When the amount exceeds 10.0 parts by weight, on the otherhand, a large amount of an unreacted modifier (b) remains in thefunctionalized polyphenylene ether resin, becoming a cause of silverstreaks upon molding.

[0043] In the invention, the temperature for reacting the polyphenyleneether (a) with the modifier (b) is from room temperature to the meltingpoint of (a). When the reaction temperature is less than roomtemperature, the polyphenylene ether (a) does not react sufficientlywith the modifier (b). Here, room temperature means 27° C. At a reactiontemperature exceeding the melting point of the polyphenylene ether (a),(a) is molten and a viscosity increase occurs, which disturbs mixingwith the modifier (b) and, in turn, smooth progress of the reaction. Atthis time, when the reaction is forcibly caused to progress by vigorouskneading of (a) and (b), the color tone of the polyphenylene ether (a)is deteriorated by heat generated upon kneading.

[0044] Moreover, the reaction temperature is preferably from roomtemperature to the glass transition temperature of the polyphenyleneether (a). A particularly preferred range is 100 to 230° C., with arange of 120 to 220° C. being most preferred.

[0045] In the invention, the reaction pressure preferably ranges from 0to 2 MPa, with a range of 0 to 1 MPa being considerably preferred.

[0046] In the invention, the functionalized polyphenylene ether resin(A) is preferably in a solid form and more preferably is a powder havingan average particle size of 10 to 500 μm. Here, the term “averageparticle size” means the size of the most fine sieve among the sieves onwhich 50% of the whole powder weight remains and it is measured byclassifying the powder into each particle size through shaking sieves,and weighing the powder left on each of these sieves. The functionalizedpolyphenylene ether resin (A) has more preferably an average particlesize of 20 to 400 μm, with 50 to 300 μm being still more preferred. Thepowder having an average particle size less than 10 μm is difficult tohandle because of the problems such as flying. The powder having anaverage particle size greater than 500 μm is, on the other hand, notpreferred, because the color tone of a molded product, less generationof black foreign matter, heat resistance and flame retardancy cannot beattained simultaneously at a sufficient level compared with thoseattained by the resin composition of the invention.

[0047] Although no particular limitation is imposed on the reactionmethod of the polyphenylene ether (a) and the modifier (b) in theinvention, preparation using a paddle drier as a reactor is preferred.Efficient preparation can be accomplished using a paddle drier having ajacket set at a desired temperature.

[0048] For preparation, use of a Henschel mixer as a reactor is morepreferred. Use of a Henschel mixer permits efficient preparation of thefunctionalized polyphenylene ether resin of the invention, because thepolyphenylene ether (a) can be mixed efficiently with the modifier (b)and at the same time, heating is effected by shear heat so thattemperature can be controlled. The modifier (b) may be circulated andreacted in the gaseous form.

[0049] The functionalized polyphenylene ether resin (A) of the inventioncan be prepared by adding thereto a reaction assistant. As this reactionassistant, a radical generator, acid, base, organic salt and inorganicsalt are preferred. Examples of the radical generator include dialkylperoxides, diacyl peroxides, peroxycarbonates, hydroperoxides andperoxyketals.

[0050] The functionalized polyphenylene ether resin (A) of the inventionmay be a polyphenylene ether having substantially all the molecularchains thereof functionalized or a polyphenylene ether having, mixedtherein, unfunctionalized polyphenylene ether molecular chains andfunctionalized polyphenylene ether molecular chains. From the viewpointof color tone and less generation of foreign matter, a ratio of thefunctionalized polyphenylene ether molecular chains to all the molecularchains is preferably 70% or greater, more preferably 80% or greater,still more preferably 90% or greater and still more preferably 95% orgreater.

[0051] To 100 parts by weight of the polyphenylene ether (a), themodifier (b) is preferably added in an amount of 0.01 to 10.0 parts byweight. This amount is more preferably 0.1 to 5.0 parts by weight, stillmore preferably 0.1 to 1.0 parts by weight. Amounts less than 0.01 partby weight are insufficient for alloying with the component (B). Amountsgreater than 10.0 parts by weight, on the other hand, become a cause forlowering of heat resistance or deterioration of color tone of a moldedproduct available from the resin composition of the invention.

[0052] The functionalized polyphenylene ether resin (A) of the inventionmay contain an aromatic vinyl polymer within an extent not damaging thecharacteristics of the invention. Examples of the aromatic vinyl polymerinclude atactic polystyrene, syndiotactic polystyrene, high impactpolystyrene and acrylonitrile-styrene copolymer. When a mixture of apolyphenylene ether resin and an aromatic vinyl polymer is used, theamount of the polyphenylene ether resin is, from the viewpoint of heatresistance, at least 70 wt. %, preferably 80 wt. %, more preferably atleast 90 wt. % based on the total amount of the polyphenylene etherresin and aromatic vinyl polymer.

[0053] As the liquid-crystal polyester (B) of the invention, knownpolyesters which are called “thermotropic liquid-crystal polymers” canbe used. Examples thereof include thermotropic liquid-crystal polyestershaving, as a main constitutional unit, p-hydroxybenzoic acid andpolyethylene terephthalate, thermotropic liquid-crystal polyestershaving, as a main constitutional unit, p-hydroxybenzoic acid and2-hydroxy-6-naphthoic acid and thermotropic liquid-crystal polyestershaving, as a main constitutional unit, p-hydroxybenzoic acid,4,4′-dihydroxybiphenyl and terephthalic acid. No particular limitationis imposed on them. As the liquid-crystal polyesters (B) to be used inthe invention, those having the following structural units (i) and (ii),and optionally (iii) and/or (iv) are preferred.

 O—X—O  (iii)

OC—X—CO  (iv)

[0054] In the above-described formulas, the structural units (i) and(ii) are a structural unit of polyester prepared from p-hydroxybenzoicacid and a structural unit prepared from 2-hydroxy-6-naphthoic acid. Useof these structural units (i) and (ii) makes it possible to obtain athermoplastic resin composition of the invention having excellent heatresistance and fluidity and being well balanced in mechanical propertiessuch as rigidity. As X in the above-described structural units (iii) and(iv), one or more than one can be selected freely from the followingformulas (3).

[0055] Preferred as the structural formula (iii) is a structural unitprepared from ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl,2,6-dihydroxynaphthalene or bisphenol A, of which that from ethyleneglycol, 4,4′-dihydroxybiphenyl or hydroquinone is more preferred, withthat from ethylene glycol or 4,4′-dihydroxybiphenyl being particularlypreferred. Preferred as the structural formula (iv) is a structural unitprepared from terephthalic acid, isophthalic acid or2,6-dicarboxynaphthalene, of which that from terephthalic acid orisophthalic acid is more preferred.

[0056] As the structural formula (iii) or (iv), one or more than onestructural units exemplified above may be used in combination. Morespecifically, when at least two structural units are used incombination, examples of the combination for the structural formula(iii) include 1) a structural unit prepared from ethylene glycol/astructural unit prepared from hydroquinone, 2) a structural unitprepared from ethylene glycol/a structural unit prepared from4,4′-dihydroxybiphenyl, 3) a structural unit prepared fromhydroquinone/a structural unit prepared from 4,4′-dihydroxybiphenyl.

[0057] Examples of the combination for the structural formula (iv)include 1) a structural unit prepared from terephthalic acid/astructural unit prepared from isophthalic acid and 2) a structural unitprepared from terephthalic acid/a structural unit prepared from2,6-dicarboxynaphthalene. In these two components, the amount ofterephthalic acid is preferably 40 wt. % or greater, more preferably 60wt. % or greater and especially 80 wt. % or greater. By setting theamount of terephthalic acid at 40 wt. % or greater in the twocomponents, the resulting resin composition has relatively good fluidityand heat resistance. Although there is no particular limitation imposedon the using ratio of the structural units (i), (ii), (iii) and (iv) inthe liquid-crystal polyester component (B), the structural units (iii)and (iv) are used essentially in an equimolar amount.

[0058] A structural unit (v) made of structural units (iii) and (iv) canbe used as the structural unit in the component (B). Specific examplesinclude 1) a structural unit prepared from ethylene glycol andterephthalic acid, 2) a structural unit prepared from hydroquinone andterephthalic acid, 3) a structural unit prepared from4,4′-dihydroxybiphenyl and terephthalic acid, 4) a structural unitprepared from 4,4′-dihydroxybiphenyl and isophthalic acid and 5) astructural unit prepared from bisphenol A and terephthalic acid.

O—X—OCO—X—CO  (v)

[0059] Into the liquid-crystal polyester component (B) of the invention,another structural unit prepared from an aromatic dicarboxylic acid,aromatic diol or aromatic hydroxycarboxylic acid can be introduced asneeded within a range of a small amount not damaging the object of theinvention. A temperature at which the component (B) starts indicating aliquid crystal condition in a molten state (which will hereinafter becalled “liquid-crystal starting temperature”) is preferably 150 to 350°C., more preferably 180 to 320° C., particularly preferably 200 to 300°C. By adjusting the liquid-crystal starting temperature to this range,the resin composition thus obtained has favorable color tone and is wellbalanced in heat resistance and moldability. The liquid-crystal startingtemperature set at 150 to 270° C. is preferred particularly for theappearance of the molded product of the resulting resin composition. Inaddition, when the liquid-crystal starting temperature is set at 250 to350° C., the abrasion resistance, chemical resistance, rigidity, creepresistance and rib strength at high temperature of the resulting resincomposition can be maintained in a preferable range.

[0060] The heat distortion temperature (under a load of 1.82 MPa, inaccordance with ASTM D648) of the component (B) of the invention ispreferably 130 to 300° C., more preferably 150 to 280° C., particularlypreferably 170 to 270° C. By adjusting the heat distortion temperaturewithin the above-described range, the resulting resin composition hasdesirable heat resistance and relatively good balance in mechanicalproperties. When the heat distortion temperature is adjusted within arange of 130 to 270° C., the resulting resin composition is impartedwith relatively good moldability and hinge properties and is reduced inboss cracks. When the heat distortion temperature is adjusted within arange of 210 to 300° C., the resulting resin composition is impartedwith relatively good creep resistance and rigidity at high temperatureand a cycle of injection molding can be shortened comparatively.

[0061] The dielectric dissipation factor (tan δ) at 25° C. and 1 MHz ofthe liquid-crystal polyester component (B) of the invention ispreferably 0.03 or less, more preferably 0.02 or less. The smaller thisdielectric dissipation factor, the smaller a dielectric loss, whichmakes it possible to suppress generation of an electric noise when theresin composition is used as a raw material for electric-electronicparts. Particularly at 25° C. in a high-frequency region, that is, in aregion of 1 to 10 GHz, the dielectric dissipation factor (tan 8) ispreferably 0.03 or less, more preferably 0.02 or less.

[0062] The apparent melt viscosity (shear rate: 100/sec atliquid-crystal starting temperature +30° C.) of the liquid-crystalpolyester component (B) of the invention is preferably 100 to 30000poises, more preferably 100 to 20000 poises, particularly 100 to 10000poises. By adjusting the apparent melt viscosity within this range, theresulting resin composition has preferable fluidity. The thermalconductivity of the component (B) of the invention under a molten state(liquid-crystal state) is preferably 0.1 to 2.0 W/mK, more preferably0.2 to 1.5 W/mK, especially 0.3 to 1.0 W/mk. Adjustment of the thermalconductivity under a molten state (liquid-crystal state) within thisrange makes it possible to relatively shorten the injection moldingcycle of the resulting resin composition.

[0063] In the invention, the functionalized polyphenylene ether resincomposition (A) is added in an amount of 99 to 1 wt. %, preferably 99 to10 wt. %, more preferably 80 to 20 wt. %. At an amount exceeding 99 wt.,the moldability drastically lowers, while at an amount less than 1 wt.%, the functional group of the component (A) does not exhibit itsefficacy and sufficient compatibilizing effects are not available.

[0064] The liquid-crystal polyester as the component (B) of theinvention is added in an amount of 1 to 99 wt. %, preferably 10 t 90 wt.%, more preferably 20 to 80 wt. %. Amounts exceeding 99 wt. % impairexhibition of surface smoothness, causing lowering in appearance and inaddition, increase a cost. At an amount less than 1 wt. %, on the otherhand, sufficient moldability is not available.

[0065] The compound containing a polyvalent metal element (C) in theinvention is a compound containing a metal element which may bemonovalent, divalent or trivalent. The compound (C) containing amonovalent, divalent and trivalent metal element in the invention is ametal-containing inorganic compound or organic compound. Moreover, thecomponent (C) of the invention is essentially a compound having a metalelement as a main component.

[0066] Specific examples of the metal element which may be monovalent,divalent or trivalent include Li, Na, K, Zn, Cd, Sn, Cu, Ni, Pd, Co, Fe,Ru, Mn, Pb, Mg, Ca, Sr, Ba and Al elements. Among them, Zn, Sn, Mg, Cdand Al are preferred, with the Zn element being more preferred. Specificexamples of the compound containing a metal element which may bemonovalent, divalent or trivalent include oxides, sulfides and aliphaticcarboxylates of the above-exemplified metal elements. Specific examplesof the oxides include LiO₂, Na₂O, K₂O, ZnO, CdO, SnO, CuO, Cu₂O, NiO,PdO, CoO, FeO, Fe₂O₃, RuO, RuO₄, MnO, MnO₂, PbO, MgO, CaO, SrO, BaO andAl₂O₃. Specific examples of the sulfides include Li₂S, Na₂S, K₂S, ZnS,CdS, SnS, CuS, Cu₂S, NiS, PdS, CoS, FeS, Fe₂S₃, RuS, RuS₄, MnS, MnS₂,PbS, MgS, CaS, SrS, BaS and Al₂S₃. Examples of the aliphaticcarboxylates include lithium stearate, sodium stearate, potassiumstearate, zinc stearate, cadmium stearate, tin stearate, copperstearate, nickel stearate, palladium stearate, cobalt stearate, ferrousstearate, ferric stearate, ruthenium stearate, manganese stearate, leadstearate, magnesium stearate, calcium stearate, strontium stearate,barium stearate and aluminum stearate. Among them, preferred are ZnO,ZnS, zinc stearate, CdO, MgO and Al₂O₃.

[0067] In the invention, the amount of the compound (C) containing apolyvalent metal element is preferably 0.001 to 5 parts by weight, morepreferably 0.01 to 3 parts by weight, still more preferably 0.1 to 1part by weight based on 100 parts by weight, in total, of the components(A) and (B). Co-existence of this component (C) drastically improvesimpact resistance, particularly, brings about a marked improvement indart drop impact. When the amount of the component (C) is less than0.001 part by weight, sufficient effects for improving impact resistanceare not available. Amounts exceeding 5 parts by weight, on the otherhand, only cause an increase in the specific gravity of the composition.

[0068] Examples of the inorganic filler (D), as a strength impartingagent, in the invention include inorganic compounds such as glassfibers, metal fibers, potassium titanate, carbon fibers, siliconcarbide, ceramics, silicon nitride, mica, nepheline syenite, talc,wollastonite, slag fibers, ferrite, glass beads, glass powder, glassballoon, quartz, quartz glass, titanium oxide and calcium carbonate.Among them, glass fibers and carbon fibers are preferred for balanceamong fluidity, heat resistance and mechanical properties. Glass fibersare more preferred. No limitation is imposed on the shape of suchinorganic fillers and free selection from fibrous, plate-type andspherical inorganic fillers is possible.

[0069] Two or more inorganic fillers exemplified above can be used incombination. If necessary, the inorganic fillers may be provided for useafter pretreatment with a coupling agent such as silane and titaniumone.

[0070] The amount of the inorganic filler (D) is added in an amount of0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, morepreferably 2 to 20 parts by weight based on 100 parts by weight, intotal, of the components (A) and (B). Amounts less than 0.1 can noteasily impart the resin composition with sufficient rigidity and heatresistance, while amounts exceeding 200 parts by weight can not easilyimpart the resin composition with sufficient fluidity.

[0071] In the invention, another additional component can be added,together with the above-described components, as needed within an extentnot impairing the characteristics and advantages of the invention.Examples include antioxidants, flame retardants (such as organicphosphate ester compounds, inorganic phosphorus compounds and aromatichalogen flame retardants), elastomers (such as ethylene/propylenecopolymer, ethylene/1-butene copolymer,ethylene/propylene/non-conjugated diene copolymer, ethylene/ethylacrylate copolymer, ethylene/glycidyl methacrylate copolymer,ethylene/vinyl acetate/glycidyl methacrylate copolymer,ethylene/propylene-maleic anhydride copolymer, olefin copolymer, e.g.,ABS, polyester polyether elastomer, polyester polyester elastomer, blockcopolymer of aromatic vinyl compound and conjugated diene compound, andhydrogenated block copolymer of aromatic vinyl compound and conjugateddiene compound), plasticizers (such as oil, low-molecular-weightpolyethylene, epoxydized soybean oil, polyethylene glycol and fatty acidester), flame retardants, weather(light)-resistance improvers,nucleating agents, lubricants, inorganic conductivity imparting agents(such as conductive metal fibers, conductive carbon black and carbonblack), various colorants and mold releasing agents.

[0072] The resin composition of the invention can be prepared in variousmanners. For example, it can be prepared by melt-kneading with heatusing a single-screw extruder, twinscrew extruder, roll, kneader,Brabender Plastograph or Banbury mixer. Among them, melt-kneading usinga twin-screw extruder is most preferred. Although no particularlimitation is imposed on the melt-kneading temperature, it can usuallybe selected freely from 150 to 300° C.

[0073] The resin composition can also be prepared by charging thepolyphenylene ether (a) and the modifier (b) from a first feed port ofan extruder, controlling the temperature inside of the extruder at aposition between the first feed port to a second feed port, therebykneading and reacting the mixture at a temperature of from roomtemperature or greater but not greater than the melting point of (a) toprepare a functionalized polyphenylene ether resin (A), setting atemperature upstream of the second feed port at a temperature permittingmelting of both the components (A) and (B), charging a liquid-crystalpolyester (B) from the second feed port and melt-kneading thefunctionalized polyphenylene ether (A), the liquid-crystal polyester (B)and the like in the extruder.

[0074] The resin composition thus obtained can be molded into variousparts in a conventionally known manner such as injection molding,extrusion molding and blow molding. Such molded products are excellentin the balance of heat resistance, flame retardancy and fluidity andthey are called “heat-resistant parts” in the invention. They areparticularly suitable for applications requiring heat resistance andflame retardancy such as heat resistant parts for automobiles and officemachines. Examples of the heat resistant parts for automobiles includealternator terminal, alternator connector, IC regulator, potentiometerbase for light dimmer, various valves such as exhaust gas valve, jointof engine coolant, carburetor main body, carburetor spacer, exhaust gassensor, coolant sensor, oil temperature sensor, brake pad wear sensor,throttle position sensor, crank shaft position sensor, air flow meter,brake pad abrasion sensor, thermostat base for air conditioner, flowcontrol valve of heater hot-air, brush holder for radiator motor, waterpump impeller, turbine vane, wiper motor parts, distributor, starterswitch, starter relay, wire harness for transmission, window washernozzle, air conditioner panel switch substrate, fuse connector, hornterminal, insulating plate for electrical components, step motor rotor,brake piston, solenoid bobbin, engine oil filter, parts such as ignitiondevice case, wheel cap, lamp socket, lamp housing, lamp extension andlamp reflector. Among them, lamp extension, and lamp reflector arepreferred for balance among light weightness, heat resistance, flameretardancy and mechanical properties. As the heat resistant parts foroffice machines, parts of household or office electric appliancestypified by parts of air conditioner, parts of typewriter and parts ofword processor; office-computer-related parts; telephone-related parts;facsimile related parts; and copying-machine-related parts arepreferred. Among them, peripheral parts of a toner fixing roll of acopying machine are preferred in consideration of the balance among heatresistance, flame retardancy, mechanical properties and specificgravity. Parts obtained by molding a resin composition of the inventionadded with a conductivity imparting agent are suited as a separator forfuel cell because they A are excellent in conductivity, fluidity, heatresistance and flame retardancy.

[0075] Reasons why the resin composition of the invention is excellentin physical properties, particularly, excellent in color tone and lessgeneration of black foreign matter has not been clarified completelyyet, but they can be presumed for example as follows. Specifically, inorder to functionalize a polyphenylene ether, a high temperature processis required in the conventional melting method, which modifies thefunctional group further or induces side reactions such as transferreaction of polyphenylene ether molecular chains and causes a change inmolecular weight, coloration or generation of black foreign matter. Inthe invention, on the other hand, the composition is functionalized at atemperature not greater than the melting point of the polyphenyleneether, that is, at a relatively low temperature so that undesirable sidereactions of the polymer are suppressed. In addition, it can also bepresumed that the functional group of the functionalized polyphenyleneether resin (A) maintains high reactivity without being deactivated andmutual action between the functional group and a hydroxyl or carboxylgroup of the liquid-crystal polyester (B) is improved.

EXAMPLES

[0076] The present invention will hereinafter be described based onExamples. It should however be borne in mind that the invention is notlimited to the following Examples insofar as it does not depart from thescope of the invention.

Preparation Example 1 Preparation Example of FunctionalizedPolyphenylene Ether (PPE-1)

[0077] a-1: Polyphenylene ether (which ispoly(2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of0.43 and obtained by oxidation polymerization of 2,6-dimethyl phenol andwhich exhibited a single peak and had a melting point of 250° C., whenmeasured using a differential scanning calorimeter (DSC) assuming that apeak top temperature of the temperature-heat flow graph obtained at aheating rate of 20° C./minute is designated as a melting point.)

[0078] b-1: Maleic anhydride

[0079] In an autoclave equipped with a thermometer for measuring theinside temperature, an oil jacket, and a gas inlet with an agitator, 10kg of the polyphenylene ether (a-1) and 0.05 kg of the modifier (b-1)were charged. At room temperature, an inside pressure was reduced to 10mmHg through the gas inlet, followed by introduction of nitrogen of anatmospheric pressure to charge the inside with nitrogen.

[0080] After repetition of the above-described operation three times,the autoclave was hermetically sealed. The (a-1) and (b-1) dischargedfrom the system upon pressure reduction and nitrogen purging werecollected. The (a-1) and (b-1) discharged from the system were found tobe 0.1 kg and 0.008 kg, respectively.

[0081] An oil set at 200° C. was circulated through the oil jacket tooperate the agitator and stirring was continued for 1 hour. After oilcirculation was stopped and the autoclave was allowed to stand until theinside temperature became room temperature, the autoclave was opened andthe contents (c-1) in the powdery form were collected. It was found thatthe contents did not contain molten substances and the mass of thecontents (c-1) was 10.0 kg.

[0082] The contents (c-1) were washed with 50 liter of acetone, followedby filtration through a filter. This operation was repeated five timesto obtain the washed substance 1 (d-1) and filtrate 1 (e-1). Analysisresults of gas chromatogram revealed that the modifier (b-1) containedin the filtrate 1 (e-1) was 0.005 kg. A 20 g portion of a driedsubstance obtained by drying of the washed substance 1 (d-1) wassubjected to reflux extraction from 40 ml of acetone by using a Soxhletextractor, whereby a washed substance 2 (g-1) with hot acetone and anextract (h-1) were obtained. Analysis results of gas chromatogramrevealed that no modifier (b-1) was contained in the extract (h-1).

[0083] The dried substance 1 (f-1) was inserted between a laminate of apolytetrafluoroethylene sheet, aluminum sheet and iron sheet which hadbeen stacked in this order and then compression molded at 10 MPa,whereby a film (i-1) was obtained. By similar operations, a film (a-1)was obtained from the polyphenylene ether (a-1). The infraredspectroscopic analysis of the resulting film (i-1) was made using a“FT/IR-420 model” Fourier transform infrared spectrophotometermanufactured by Nippon Bunkosha Co., Ltd., resulting in observation, at1790 cm⁻¹, of a peak derived from maleic acid added to the polyphenyleneether. The amount of the modifier (b-1) added to the polyphenylene etherwas found to be 0.31 part by weight.

[0084] This dried substance 1 (f-1) was provided for Examples as thefunctionalized polyphenylene ether (PPE-1). It was found to have anaverage particle size of 110 μm.

Preparation Example 2 Preparation Example of FunctionalizedPolyphenylene Ether (PPE-2)

[0085] In a similar manner to Preparation Example 1 except for theaddition of 0.3 part by weight of2,5-dimethyl-2,5-bis(t-butylperoxy)hexane upon charging, thefunctionalized polyphenylene ether (PPE-2) was obtained. It wasconfirmed that the resulting product had the modifier (b-1) addedthereto in an amount of 0.40 part by weight and had an average particlesize was 140 μm.

Preparation Example 3 Preparation Example of FunctionalizedPolyphenylene Ether (PPE-3)

[0086] In an autoclave tank, 0.5 kg of the modifier (b-1) was chargedand the autoclave was pipe-connected with a “FM10C/I model” Henschelmixer manufactured by Mitsui Mining Co., Ltd. In the Henschel mixer, 2kg of the polyphenylene ether (a-1) in the powdery form was charged. Itwas stirred at 600 rpm while the tank was purged with a nitrogen gasstream. An oil of 200° C. was fed to the jacket of the mixer, and thepolyphenylene ether (a-1) powder was heated until it became 190° C. Theautoclave tank was then put into an oil bath to adjust the temperatureof the modifier (b-1) in the tank at 190° C. When the temperatures ofthe polyphenylene ether (a-1) powder and modifier (b-1) became stable at190° C., 1 L/min of nitrogen was fed from the autoclave tank to thedirection of the Henschel mixer and a gas mixture of the modifier (b-1)and nitrogen was fed to the Henschel mixer. At this time, the outletvalve of the Henschel mixer for nitrogen was opened to permit continuouscirculation of the gas mixture of the modifier (b-1) and nitrogen.Without changing the condition, stirring and gas circulation werecontinued for 20 minutes. Twenty minutes later, the oil of 200° C. wastaken out from the jacket and instead, an oil of room temperature wasfed to cool the polyphenylene ether powder in the mixer tank to roomtemperature. The a polyphenylene ether powder thus obtained wasextracted from hot acetone as in Example 1 to remove the unreactedmodifier (b-1), whereby the functionalized polyphenylene ether (PPE-3)was obtained. It was confirmed that the resulting product had themodifier (b-1) added thereto in an amount of 0.56 part by weight and hadan average particle size of 120 μm.

Referential Example 1 Referential Example of Polyphenylene Ether (PPE-4)

[0087] The polyphenylene ether (a-1) powder which was a raw materialemployed in Preparation Example 1 was designated as the polyphenyleneether (PPE-4). Its average particle size was found to be 90 μm.

Referential Example 2 Referential Example of Polyphenylene EtherModified by Melting (PPE-5)

[0088] A reaction was conducted by melt-kneading 100 parts by weight ofthe polyphenylene ether (a-1) and 1 part by weight of the modifier (b-1)in a twin screw extruder (“ZSK-25”, manufactured by WERNER & PFLEIDERERCorp.) set at 300° C. and equipped with a vent port. The pellets thusobtained were pulverized, followed by washing with acetone, whereby thepolyphenylene ether modified by melting (PPE-5) was obtained. It wasconfirmed that the resulting product had the modifier (b-1) addedthereto in an amount of 0.41 part by weight and had an average particlesize of 900 μm.

Preparation Example 4 Preparation Example of Liquid-crystal Polyester(LCP-1)

[0089] Under a nitrogen atmosphere, p-hydroxybenzoic acid,2-hydroxy-6-naphthoic acid and acetic anhydride were charged, followedby melting under heat and polycondensation, whereby the liquid-crystalpolyester (LCP-1) having the below-described theoretical structuralformula was obtained. The component ratio of the composition isindicated by a molar ratio.

Preparation Example 5 Preparation Example of Liquid-crystal Polyester(LCP-2)

[0090] Under a nitrogen atmosphere, p-hydroxybenzoic acid, polyethyleneterephthalate and acetic anhydride were charged, followed by meltingunder heat and polycondensation, whereby the liquid-crystal polyester(LCP-2) having the below-described theoretical structural formula wasobtained. The component ratio of the composition is indicated by a molarratio.

Preparation Example 6 Preparation example of Liquid-crystal Polyester(LCP-3)

[0091] Under a nitrogen atmosphere, p-hydroxybenzoic acid,2-hydroxy-6-naphthoic acid, polyethylene terephthalate and aceticanhydride were charged, followed by melting under heat andpolycondensation, whereby the liquid-crystal polyester (LCP-3) havingthe below-described theoretical structural formula was obtained. Thecomponent ratio of the composition is indicated by a molar ratio.

Preparation Example 7 Preparation Example of Liquid-crystal Polyester(LCP-4)

[0092] Under a nitrogen atmosphere, p-hydroxybenzoic acid,2-hydroxy-6-naphthoic acid, hydroquinone, isophthalic acid and aceticanhydride were charged, followed by melting under heat andpolycondensation, whereby the liquid-crystal polyester (LCP-4) havingthe below-described theoretical structural formula was obtained. Thecomponent ratio of the composition is indicated by a molar ratio.

Referential Example 3 Referential Example of Master Batch Pellets as anAdditive

[0093] After dry blending of 23 parts by weight oftris(2,4-di-t-butylphenyl)phosphite (“Mark 2112”, product of Asahi DenkaKogyo K. K.), 23 parts by weight of zinc oxide (JIS Special Grade,product of Wako Pure Chemicals Industries, Ltd.), 23 parts by weight ofzinc sulfide (JIS Special Grade, product of Wako Pure ChemicalIndustries, Ltd.) and 31 parts by weight of polystyrene (“H9405”,product of A&M Styrene Co., Ltd.), the mixture was melt-kneaded by atwin screw extruder (“ZSK-25”, manufactured by WERNER & PFLEIDERERCorp.) set at 230° C. and equipped with a vent port, whereby masterbatch pellets were obtained as a stabilizer. These pellets were providedfor Examples as a stabilizer (hereinafter abbreviated as “MB”).

[0094] Physical properties of each of the resin compositions were eachevaluated in the following manner.

[0095] (1) Molding:

[0096] The pellets obtained in Examples or Comparative Examples weremolded using an injection molder [“IS˜80EPN”, manufactured by ToshibaMachine Co., Ltd.] set at a cylinder temperature of 330/330/320/310° C.,injection rate of 85% and mold temperature of 90° C. The pelletsobtained in Examples 10 and 11 and Comparative Example 4 were howevermolded at a cylinder temperature of 275/275/265/255° C., injection rateof 60% and mold temperature of 70° C.

[0097] (2) Color Tone:

[0098] The pellets were molded into a plate piece of 90 mm long, 50 mmwide and 2.5 mm thick and L, a and b of the molded product at 23° C.were measured using a calorimeter (“ZE2000”, product of Nippon DenshokuKogyo Co., Ltd.). In accordance with the below-described equation,whiteness: W (Lab) was calculated. The higher whiteness means bettercolor tone.

W (Lab)=100−((100−L)² +a ² +b ²)^(½)

[0099] (3) Less Generation of Black Foreign Matter:

[0100] After retention for 5 minutes upon molding, a plate of 90×50×2.5mm was molded under the above-described conditions (1). The resultingmolded plate was pulverized and the whole amount was dissolved in 100 mlof chloroform. The solution was filtered through a filter paper of 10 cmin diameter. After completion of the filtration, the number of blackforeign matter(s) was counted with the naked eye. The white solid wasliquid-crystal polyester or inorganic filler insoluble in chloroform soit was not counted.

[0101] (4) Fluidity:

[0102] A gauge pressure when a 1-mm short appeared upon molding of thepellets obtained in the Examples into an ASTM dumbbell specimen of 3.2mm thick under the molding conditions described above in (1) wasmeasured. In the below-described table, this pressure is expressed asSSP (MPa), (abbreviation of Short Shot Pressure).

[0103] (5) Heat Resistance (DTUL):

[0104] The pellets obtained in the Examples were molded into an ASTMstrip specimen of 3.2 mm thick under the molding conditions describedabove in (1). Heat distortion temperature of the resulting specimen wasmeasured under a load of 1.82 MPa.

[0105] (6) Flame Retardancy:

[0106] An ASTM strip specimen of 1.6 mm thick×127 mm long×12.7 mm widewas obtained by molding and a burning test was conducted based on UL-94Vertical Burning Test of Underwriters Laboratories. Describedspecifically, this burning test was made on five specimens. Assumingthat a time from removal of a flame after ignition of each specimentherewith for 10 seconds until extinction of the flame is a combustiontime t₁ (second) and a time from removal of a flame after ignition ofthe specimen therewith again for 10 seconds until extinction of theflame is a combustion time t₂ (second), an average combustion time of t₁and t₂ of each of five specimens was determined. In addition, it wasrated as V-0, V-1 or V-2 in accordance with the UL standards.

[0107] (7) Flexural Properties:

[0108] A bending test of an ASTM strip specimen of 3.2 mm thick wasconducted at a span distance of 50 mm and test speed of 3 mm/min byusing an autograph (“AG-5000”, product of Shimadzu Corporation), wherebya flexural modulus (FM) and flexural strength (FS) were measured.

[0109] (8) Tensile Properties:

[0110] A tensile test of an ASTM dumbbell specimen of 3.2 mm thick wasconducted at a chuck distance of 115 mm and test speed of 20 mm/min byusing an autograph (“AG-5000”, product of Shimadzu Corporation), wherebya tensile modulus (TM) and tensile strength (TS) were measured.

[0111] (9) Impact Resistance:

[0112] (9-1) Dart Impact and Ductile Fracture:

[0113] Measurement of the specimen similar to that employed in the above(2) was conducted under a dropping load of 6.5 kg and drop height of 100cm by using a dart impact tester (product of Toyo Seiki Co., Ltd.) andwhole absorption energy, which is the sum of cracking energy andpropagation energy upon fracture was designated as a dart impact (J/m).The greater the dart impact, the better impact resistance. When a platespecimen is observed from a thickness direction after the fracture test,a state wherein deformation as if hammered thin has occurred at the dartdropped part is defined as ductile fracture, while a state whereincomplete gouging has occurred at the dart dropped part but the testpiece is flat without deformation is defined as brittle fracture. Basedon the above-described standards, ductile fracture was judged. Thenumber of tests was set at n=5.

[0114] ◯: Ductile fracture occurred at any test n=5.

[0115] Δ: Ductile fracture occurred 1 to 4 times of n=5, while brittlefracture occurred at the remaining test(s).

[0116] x: Brittle fracture occurred at any test n=5.

Examples 1 TO 5 AND 8

[0117] The functionalized polyphenylene ether (PPE-1, PPE-2 or PPE-3)and the liquid-crystal polyester (LCP-1, LCP-2, LCP-3 or LCP-4) weremelt-kneaded at a ratio (parts by weight) as shown in Table 1 by using atwin-screw extruder (“ZSK-25”, product of WERNER & PFLEIDERER Corp.) setat 250 to 300° C. and equipped with a vent port. The pellets thusobtained were molded in the above-described manner and physicalproperties of the molded product were evaluated. The results are shownin Table 1.

Examples 6, 9 AND 11

[0118] In a similar manner to Example 1 except that the functionalizedpolyphenylene ether (PPE-1 or PPE-3) as a functionalized polyphenyleneether resin and the liquid-crystal polyester (LCP-2, LCP-3 or LCP4) wereused; glass fibers (“Microglass RES03-TP30”, product of NGF Company,these glass fibers which may hereinafter be abbreviated as “GF”) wereadded by side feeding; and they were added at a ratio (parts by weight)as shown in Table 1. The pellets thus obtained were molded in theabove-described manner and physical properties of the molded productwere evaluated. The results are shown in Table 1.

Example 7

[0119] In a similar manner to Example 1 except that the functionalizedpolyphenylene ether (PPE-1) as a functionalized polyphenylene etherresin and the high impact polystyrene (“H9405”, product of A&M StyreneCo., Ltd., which styrene may hereinafter be abbreviated as “HIPS”) wereused and components were mixed at a ratio as shown in Table 1, pelletswere obtained. The resulting pellets were molded in the above-describedmanner and physical properties of the molded product were evaluated. Theresults are shown in Table 1.

Comparative Example 1

[0120] In a similar manner to Example 1 except for the use of theun-functionalized polyphenylene ether (PPE-4) was used instead of thefunctionalized polyphenylene ether (PPE-1), pellets were obtained. Theresulting pellets were molded in the above-described manner and physicalproperties of the molded product were evaluated. The results are shownin Table 1.

Comparative Example 2

[0121] In a similar manner to Example 1 except that the polyphenyleneether modified by melting (PPE-5) was used instead of the functionalizedpolyphenylene ether (PPE-1), pellets were obtained. The resultingpellets were molded in the above-described manner and physicalproperties of the molded product were evaluated. The results are shownin Table 1.

Comparative Example 3

[0122] In a similar manner to Example 1 except for the omission of aliquid-crystal polyester, pellets were obtained. The resulting pelletswere molded in the above-described manner and physical properties of themolded product were evaluated. The results are shown in Table 1.

Examples 10 AND 11

[0123] In a similar manner to Example 1 except that components were usedat a ratio as shown in Table 1 and the temperature of the twin-screwextruder equipped with a vent port was set at 170 to 275° C., pelletswere obtained. The resulting pellets were molded in the above-describedmanner and physical properties of the molded product were evaluated. Theresults are shown in Table 1.

Comparative Example 4

[0124] In a similar manner to Example 10 except for the use of theun-functionalized polyphenylene ether (PPE-4) instead of thefunctionalized polyphenylene ether (PPE-1), pellets were obtained. Theresulting pellets were molded in the above-described manner and thephysical properties of the molded product were evaluated. The resultsare shown in Table 1. TABLE 1 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 1 2 3 4 56 7 8 Com- (A) PPE-1 95 93 90 85 90 position PPE-2 95 97 PPE-3 95 PPE-4PPE-5 HIPS 5 (B) LCP-1 5 4 10 4 2.5 LCP-2 3 2.5 LCP-3 3 5 5 LCP-4 1 10(D) GF 2 Physi- Color tone white- 59.3 62.8 62.9 58.8 53.3 69.4 62.263.3 cal ness W proper- (Lab) ties Less generation of 15 8 6 12 19 9 1614 black foreign matter Fluidity SSP 5.2 5.1 4.3 5.2 5.3 3.2 3.5 4.9(MPa) Heat DTUL 185 183 181 184 185 185 179 185 resistance (° C.) FlameAverage 7.4 12 8.0 8.0 9.3 4.9 8.8 7.8 retardancy combus- tion time(sec) (UL) V-1 V-1 V-1 V-1 V-1 V-0 V-1 V-1 Bending FM 2.77 2.89 3.042.80 2.73 3.21 2.69 2.99 properties (GPa) FS 114 126 120 121 112 128 110117 (MPa) Tensile TM 1.76 1.83 2.02 1.73 1.74 2.21 1.71 1.79 properties(GPa) TS 78 77 66 74 78 81 68 79 (MPa) Com. Com. Com. Ex. Ex. Com. Ex.9Ex.1 Ex.2 Ex.3 10 11 Ex.4 Com- (A) PPE-1 100 40 position PPE-2 40 PPE-380 PPE-4 95 40 PPE-5 95 HIPS (B) LCP-1 5 5 60 60 LCP-2 10 LCP-3 10 LCP-460 (D) GF 10 20 Physi- Color tone white- 71.1 50.4 48.6 6.9 79.2 78.465.2 cal ness W proper- (Lab) ties Less generation of 11 61 88 103 2 531 black foreign matter Fluidity SSP 3.6 5.7 5.5 8.3 2.2 3.1 2.8 (MPa)Heat DTUL 186 182 182 185 174 187 175 resistance (° C.) Flame Average6.2 8.5 13 11 4.2 3.5 4.1 retardancy combus- tion time (sec) (UL) V-1V-1 V-1 V-1 V-0 V-0 V-0 Bending FM 3.52 2.80 2.79 2.52 6.37 8.78 6.47properties GPa FS 127 121 123 111 143 181 147 (MPa) Tensile TM 2.22 1.731.76 1.84 2.85 3.32 2.80 properties (GPa) TS 84 74 74 73 113 129 114(MPa)

[0125] As shown in Table 1, it has been understood that resincompositions of the invention composed of a functionalized polyphenyleneether and a liquid-crystal polyester can simultaneously attainsufficient color tone, moldability, heat resistance, flame retardancyand mechanical properties and particularly, they are excellent in colortone and less generation of black foreign matter. Excellent color tonecan widen the design of molded products. Black foreign matter ispresumed to appear owing to the progress of carbonization of a portionof the resin composition upon retention under high temperature at thetime of extrusion and it may cause a lowering of insulation propertiesor physical properties. The smaller its content, the better. Inelectronic circuit parts, black foreign matter adversely affects notonly insulation properties but also dielectric loss properties. Itdisturbs transmission of electric signals, leading to fatal defects ofsuch parts. Accordingly, it has a significant meaning for polyphenyleneether resin compositions to be able to reduce a generation amount ofblack foreign matter. Even after retention upon molding, the resincompositions of the invention generate a markedly small amount of blackforeign matter, meaning excellent heat stability upon molding. Thisinvention is of a marked utility value for the industrial field.

Examples 12 to 17

[0126] In a similar manner to Examples 1 to 6 except that a compoundselected from any one of ZnO (JIS Special Grade, product of Wako PureChemical Industries, Ltd.), ZnS (JIS Special Grade, product of Wako PureChemical Industries, Ltd.), the additive master batch pellets (MB)obtained in Referential Example 3, zinc stearate (JIS Special Grade,product of Wako Pure Chemical Industries, Ltd., described as “”St₂Zn” inTable), SnO (JIS Special Grade, product of Wako Pure ChemicalIndustries, Ltd.) and MgO (JIS Special Grade, product of Wako PureChemical Industris, Ltd.) was added as a polyvalentmetal-element-containing compound (C) at a ratio as shown in Table 2,pellets were obtained. The resulting pellets were molded in theabove-described manner and physical properties of the product wereevaluated. The results are shown in Table 2.

Example 18

[0127] In a similar manner to Example 8 except for the addition of 0.15phr of ZnO (JIS Special Grade; product of Wako Pure Chemical Industries,Ltd.), pellets were obtained. The resulting pellets were molded in theabove-described manner and physical properties of the product wereevaluated. The results are shown in Table 2.

Comparative Example 5

[0128] In a similar manner to Example 12 except for the use of theun-functionalized polyphenylene ether (PPE-4) instead of thefunctionalized polyphenylene ether (PPE-1), pellets were obtained. Theresulting pellets were molded in the above-described manner and physicalproperties of the product were evaluated. The results are shown in Table2.

Comparative Example 6

[0129] In a similar manner to Example 12 except for the use of thepolyphenylene ether (PPE-5) modified by melting instead of thefunctionalized polyphenylene ether (PPE-1), pellets were obtained. Theresulting pellets were molded in the above-described manner and physicalproperties of the product were evaluated. The results are shown in Table2. TABLE 2 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Com. Com. 12 13 14 15 16 17 18Ex. 5 Ex. 6 Composition (A) PPE-1 95 93 90 85 PPE-2 95 97 PPE-3 95 PPE-495 PPE-5 95 (B) LCP-1 5 4 10 4 2.5 5 5 LCP-2 3 2.5 LCP-3 3 5 LCP-4 1 10(C) Kind ZnO ZnO MB St2Zn SnO Mgo ZnO ZnO ZnO (amount phr) (0.15) (0.15)(1.0) (0.15) (0.15) (0.30) (0.15) (0.15) (0.15) — ZnS — — — — — — —(0.15) (D) GF 2 Physical Impact resistance Dart (J/m) 54.4 52.4 54.356.1 39.1 41.0 50.4 8.6 6.4 Properties Ductile fracture ◯ ◯ ◯ ◯ Δ Δ ◯ XX Color tone Whiteness W (Lab) 61.1 64.2 85.3 80.8 55.1 70.4 62.2 51.250.3 Less generation of black foreign matter 10 14 5 10 19 7 8 85 132Fluidity SSP (MPa) 5.5 5.3 4.4 5.7 5.6 3.5 5.4 7.2 6.9 Heat resistanceDTUL (° C.) 184 183 182 182 184 185 185 182 182 Flame retardancy Averagecombustion time 7.8 8.2 9.8 11.1 8.2 7.9 8.5 11.3 17 (sec) (UL) V-1 V-1V-1 V-1 V-1 V-1 V-1 V-1 V-1 Bending properties FM (GPa) 2.78 2.92 3.112.71 2.72 3.22 2.91 2.79 2.76 FS (MPa) 111 127 122 118 114 129 115 118117 Tensile properties TM (GPa) 1.79 1.81 2.04 1.70 1.73 2.23 1.78 1.711.73 TS (MPa) 76 76 65 72 78 84 80 71 72

[0130] As shown in Table 2, it has been found that by adding a trace ofa polyvalent metal-element-containing compound to the resin compositionof the invention, more specifically, by mixing, in the solid phase,predetermined amounts of a functionalized polyphenylene ether resin,liquid-crystal polyester and polyvalent-metal-element-containingcompound, dart impact properties as well as color tone, less generationof black foreign matter, fluidity, heat resistance, flame retardancy andmechanical properties can be attained at a markedly high level.

[0131] Industrial Applicability

[0132] The present invention makes it possible to provide resincompositions having a sufficient level of color tone, moldability, heatresistance, flame retardancy and mechanical properties attainedsimultaneously and particularly, being excellent in color tone and lessgeneration of foreign matter.

1. A resin composition obtained by melt-kneading: (A) 99 to 1 wt. % of a functionalized polyphenylene ether resin obtained by reacting a mixture of: (a) 100 parts by weight of a polyphenylene ether, and (b) 0.01 to 10.0 parts by weight of a modifier selected from non-aromatic conjugated diene compounds, dienophile compounds having one dienophile group and precursors for these diene or dienophile compounds at a reaction temperature of from room temperature to the melting point of (a); and (B) 1 to 99 wt. % of a liquid-crystal polyester.
 2. The resin composition according to claim 1, wherein the functionalized polyphenylene ether resin (A) has an average particle size of 10 to 500 μm.
 3. The resin composition according to claim 1, wherein the reaction temperature for obtaining the functionalized polyphenylene ether resin (A) is within a range of from room temperature to the glass transition point of (a).
 4. The resin composition according to claim 1, wherein the reaction temperature for obtaining the functionalized polyphenylene ether resin (A) is within a range of from 120° C. to 220° C.
 5. The resin composition according to claim 1, wherein the modifier (b) is a compound having, in its molecular structure, at least one of (i) a carbon-carbon double bond and (ii) at least one of carboxyl group, oxidized acyl group, imino group, imide group, hydroxyl group and epoxy group.
 6. The resin composition according to claim 1, wherein the modifier (b) is any one of maleic anhydride, maleic acid, fumaric acid, phenyl maleimide, itaconic acid and glycidyl methacrylate.
 7. The resin composition according to claim 1, wherein the modifier (b) is maleic anhydride.
 8. The resin composition according to claim 1, which further comprises (C) 0.001 to 5 parts by weight of a compound containing a polyvalent metal element based on 100 parts by weight, in total, of (A) and (B).
 9. The resin composition according to claim 8, wherein the compound (C) containing a polyvalent metal element is at least one compound selected from ZnO, ZnS, SnO, SnS, zinc stearate, zinc acetate and MgO.
 10. The resin composition according to claim 1, which further comprises (D) 0.1 to 200 parts by weight of an inorganic filler based on 100 parts by weight, in total, of (A) and (B).
 11. The resin composition according to claim 8, which further comprises (D) 0.1 to 200 parts by weight of an inorganic filler based on 100 parts by weight, in total, of (A) and (B).
 12. A heat resistant part obtained by molding a resin composition according to any one of claims 1 to
 11. 13. A heat resistant part according to claim 12, wherein the heat resistant part is for automobiles or office machines. 